US3900493A - Polyglycidyl compounds containing n-heterocyclic structure - Google Patents

Abstract

The polyglycidyl compounds according to the invention can be manufactured by reacting epihalogenohydrin with compounds of the formula IV

OR THE FORMULA V

in which 1.) n denotes 2, 3 or 4, 2.) A represents a 2-valent, 3-valent or 4-valent organic radical which either contains a Nheterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2 phenylene rings, 3.) either B denotes the -CH2.O.CO- radical and m denotes the number 1, or B denotes the radical
and m denotes 0, and 4.) R1 represents a divalent radical, which contains at least one hydrantoin ring or uracil ring. During the reaction hydrogen halide splits off. From curable mixtures containing polyglycidyl compounds according to the invention and a curing agent such as hexahydrophthalic anhydride or phthalic anhydride are obtained products with good mechanical and electrical properties.

Description

United States Patent [1 1 Habermeier et al.

[ Aug. 19, 1975 POLYGLYCIDYL COMPOUNDS CONTAINING N-HETEROCYCLIC STRUCTURE [75] Inventors: Jiirgen Habermeier, Pfeffingen;

Hans Batzer, Arlesheim; Daniel Porret, Binningen, all of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: June 19, 1973 211 App]. NOJ 371,449

[30] Foreign Application Priority Data June 23. 1972 Switzerland 9528/72 [52] US. Cl. 260/309.5; 260/2; 260/37;

260/57; 260/69; 260/72; 260/78; 260/257; 260/260 [51] Int. Cl.. C07d 49/32; C07d 51/20; C07d 51/30 [58] Field of Search 260/309.5

[56] References Cited UNITED STATES PATENTS 3629.263 l2/l97l Batzer et al 260/257 Primary E.raminerHenry R. Jiles Assistant li.\'z. minerC. M. S. .laisle Attorney, Agent, or Firm-Vincent J. Cavalieri [57] ABSTRACT The polyglycidyl compounds according to the invention can be manufactured by reacting epihalogenohydrin with compounds of the formula IV or the formula V in which 1.) n denotes 2, 3 or 4, 2.) A represents a 2- valent, 3-valent or 4-valent organic radical which either contains a N-heterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2 phenylene rings, 3.) either B denotes the Cl-l .O.CO-- radical and m denotes the number I, or B denotes the radical cit-o eu o hydride are obtained products with good mechanical and electrical properties.

5 Claims, No Drawings POLYGLYCIDYL COMPOUNDS CONTAINING N-HETEROCYCLIC STRUCTURE The invention relates to new polyglycidyl compounds containing N-heterocyclic structures, a process for their manufacture and their use.

standards set with regard to mechanical and electrical properties.

The subject'of the invention are new polyglycidyl compounds containing N-heterocyclic structures, of the general formula I in which a and b are identical or different and denote either 0 or 1, and in which R denotes a hydrogen atom or a methyl group and R denotes a nitrogen-free, 2- valent radical which is necessary to complete a fivemembered or six-membered unsubstituted or substituted ring, or of the general formula III (III) in which 1. either B denotes the -CI-I .O.CO- radical and m denotes the number 1, or B denotes the radical /CH O cu -o andm denotes O, and 2. R has the above meaning.

In the formula I, A can represent one of the following organic molecular groups:

| C H OH CH in which 1. n denotes 2, 3 or 4, 2. A represents a 2valent, 3-valent or 4-valent organic radical which either contains a N-heterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2 phenylene rings, and 3. R represents a divalent radical of the formula II CH CH In the formula ll, R can denote one of the radicals In such a case, the polyglycidyl compounds according to the formula I or formula Ill are substances containing hydantoin rings.

R can, however, also represent one of the following divalent radicals:

or the formula V in which A, R, B, n and m have the abovementioned meaning with epihalogenohydrin, hydrogen halide being split off. Instead of epihalogenohydrin, methylepihalogenohydrin can also be employed. In that case, polyglycidyl compounds are obtained which are slightly modified by the methyl groups introduced into the molecule. Preferably, epichlorohydrin is employed.

The process according to the invention is advantageously carried out with azeotropic removal of the water in the presence of a hydrogen halide acceptor. As such it is possible to use, for example, alkali metal hydroxide, most simply sodium hydroxide in an equivalent amount or in slight excess (5 30%). If desired, a catalyst is also employed, for example a quaternary ammonium halide, such as tetramethylammonium hydroxide, teetraethylammonium bromide or benzyltrimethylammonium chloride.

It is surprising that the process according to the invention can be carried out without complications. Given the presence of the numerous active H atoms in the reaction mixture and the accumulation of the epoxide groups in the molecule of the resulting end product of the formula I or III, complications due to undesired polyaddition and premature crosslinking were to be expected.

The starting substances of the formula IV or of the formula V for the manufacture of the polyglycidyl compounds according to the invention are also new. They are substances which always contain at least 2 (namely n) secondary hydroxyl groups. In addition, they either contain n NH groups of a N-heterocyclic ring and n primary hydroxyl groups.

The manufacture of these new polyols of the formula IV or of the formula V takes place, in the former case, by reaction of appropriate diepoxide, triepoxide or tetraepoxide compounds with H-heterocyclic substances of the formula in which R and a are defined as above, to give the corresponding adduct in a manner which is in itself known,

5 there being about 2 NH groups in the reaction mixture per 1 epoxide group.

In the latter case, in which the substances of the formula 1V or of the formula V also contain primary hydroxyl groups in addition to the secondary hydroxyl groups, an identical adduct to that in the first case is initially manufactured as an intermediate product. In a 2nd stage, the NH groups contained in this adduct are then reacted further with ethylene oxide or propylene oxide in a known manner to give the particular primary alcohol.

The following may be mentioned as examples of polyepoxide compounds which are suitable for use as starting products for the polyols of the formula IV: 1- glycidyl-3-(glycidyl-2'-oxy-n-propyl)-5,5- dimethylhydantoin, 1-glycidyloxymethyl-3-glycidyl- 5,5-dimethylhydantoin, 1,1 '-methylenebis-( 3-glycidyl- 5,5-dimethylhydantoin), 1,3-diglycidyl-5,5- dimethylhydantoin, 2 ,2,6,6-tetra( glycidylcarboxyethyl)cyclohexanone, bisphenol-A diglycidyl ether or polymeric derivatives thereof. (As regards the polymeric derivatives of bisphenol-A diglycidyl ethers, it should additionally be noted that for practical purposes appropriate polymer mixtures with degrees of polymerisation of up to about 5 are concerned).

As polyepoxide compounds which are suitable for use as starting products for the polyols of the formula V, the following should be listed as examples: 3,4- epoxycyclohexylmethyl) -3, 4- epoxycyclohexanecarboxylate and 3-(3,4-epoxycyclohexyl)-2,4- dioxaspiro-(S ,5 )-9, l-epoxyundecane.

The following N-heterocyclic substances are examples of reaction partners for these polyepoxide compounds in the manufacture of the above polyols: 5,5- pentamethylenehydantoin, 5,5-dimethylhydantoin, 5- isopropylhydantoin, 5,5-diethylbarbituric acid, 1,1- methylene-bis-( 5 ,5-dimethyl-5,6-dihydrouracil 1,1 methylene-bis-( 5,5 -dimethylhydantoin), 1,1 methylene-bis-(5-isopropylhydantoin), 6-methyluraci1, 5,5-dimethyl-6-isopropyl-5,6-dihydrouraci1 and 1,2- bis-( 5 ,5-dimethylhydantoinyl-3 )-ethane.

These new polyols which may contain NI-I groups are viscous or solid, in most cases pale yellow-coloured, substances. If these are derived from polymeric bisphenol-A diglycidyl ethers, the reaction with the epihalogenohydrin leads either to polyglycidyl compounds of the formula I which still contain, unchanged, the OH groups originating from the initial diglycidyl ethers, or to polyglycidyl compounds which contain additional epoxide groups produced by reaction of these originally present OH groups with epihalogenohydrin. Furthermore, intermediate stages are also possible. The degree of reaction of the original OH groups results essentially from the amount of the epihalogenohydrin and caustic alkali in the reaction mixture. Usable polyglycidyl compounds of the formula (1) according to the invention are also obtained by starting from compounds of the formula IV in which the radical A denotes the molecular group of the formula or the molecular group of the formula OH 1 to 8 Starting substances for these special compounds of the formula IV are again the diglycidyl ethers of resorcinol or of polyethers containing several resorcinol structures.

The polyglycidyl compounds according to the invention, of the formula I and the formula III, are solid or liquid, mostly pale yellow-coloured, substances. The special feature of these substances is that they contain a relatively large number of glycidyl groups per molecule. They have epoxide contents of between about 3.0 and 8.0 mols/kg of resin and can, together with curing agents, such as dicarboxylic acid anhydrides, easily be converted into curable mixtures at temperatures of 60 C. Hexahydrophthalic anhydride and phthalic anhydride are particularly suitable as curing agents.

The curing of these mixtures, which is a further subject of this invention, in general takes place at temperatures of 80 to C. It can also be carried out stepwise at different temperatures. Ultimately, mouldings of high mechanical and electrical quality are obtained. The curable mixtures according to the invention are in particular suitable for use as compression moulding compositions and casting resins. In principle, they can also be used as lacquer resins and laminating resins.

For the manufacture, modification or processing and the like, everything known to the expert from publications and relevant patent specifications on an extensive scale applies to the mixtures according to the invention.

In the examples which follow, parts denote parts by weight and the percentages denote percentages by weight. The relationship of parts by volume to parts by weight is as of ml to g.

A. MANUFACTURING EXAMPLES Manufacture of the Starting Substances according to the Formula IV or V EXAMPLE A Adduct of 5,5-dimethylhydantoin and 1,1 '-methylene-bis-( 3-glycidyl-5,5dimethylhydantoin) 256 g of 5,5-dimethylhydantoin (2 mols) and 1.6 ml of 40% strength aqueous tetramethylammonium chloride solution are heated to 170C in a glass apparatus equipped with a stirrer, thermometer and reflux condenser and the resulting melt is stirred. 380 g of 1,1- methylene-bis-( 3-glycidyl-5 ,S-dimethylhydantoin) (5 .0 equivalent of epoxide) are added over the course of 1 hour, whilst stirring. 3 hours later, the residual epoxide content is only 0.14 equivalent/kg. The mixture is stirred for a further 5 hours at C and the adduct is poured out onto a metal sheet. A solid, clear, brittle mass of softening point 1 16C is obtained in quantitative yield. The residual epoxide content is only 0.048 equivalent/kg (corresponding to 98.3% conversion).

The content of NH groups in the 3-position of the N-heterocyclic ring is 0.17 equivalent/kg (corresponding to a conversion of 94.3% of theory). Accordingly, the product predominantly consists of:

C H T H c 3 H C CH o 3 I I I .'l H N N-cH -cH-cH o -OCH2--(II'H--CH2 N N H Y OH CH OH Y o o C H 3 H C CH 3 H c c H 3 H 0 1 ,CH "3 0 o 3 I N-N N H2C-('IHCH2-N N CH2 N N -CH2CHCH2N N -H Y Y Y 0 O o 0 EXAMPLE B EXAMPLE C Adduct of 5,5-dimethylhydantoin and bisphenol-A-diglycidyl ether A solution of 177 g of a technically manufactured bisphenol-A diglycidyl ether (Araldite MY 790) of high monomer content (5.70 epoxide equivalents/kg) (corresponding to 0.5 mol) in 500 ml of dimethylformamide is mixed with 128.2 g of 5,5-dimethylhydantoin 1 mol) and the mixture is heated to 120C whilst stirring. 1.7 g of tetraethylammonium chloride are then added, whereupon a slightly exothermic reaction commences. 1n the course thereof, the temperature rises to 130C. Thereafter, the mixture is stirred for a further 2 hours at 120C adjusted to pH=7 with a little strength sulphuric acid, filtered hot and concentrated at C/15 mm Hg. Thereafter the residue is dried to constant weight at C/0.2 mm Hg. A solid, clear, light yellow adduct is obtained in quantitative yield. This crude adduct can be purified by recrystallisation from 50% strength ethanol in the ratio 1:6. After drying, 269.8 g (88.4% of theory) of a colourless fine crystalline material which melts at 169 182C is obtained. The NMR and IR spectra show that predominantly an adduct of the following structure is present:

Adduct of methylene-bis-dimethylhydantoin and bisphenol-A diglycidyl ether 117.5 g of the bisphenol-A diglycidyl ether used in Example 2 (0.3 mol) in 700 ml of dimethylformamide are reacted with 160 g of l,1'-methylene-bis(5,5 dimethylhydantoin) (0.6 mol) at 124C, analogously to Example B. 0.9 g of tetraethylammonium chloride is used as the catalyst. The reaction is again slightly exothermic After stirring for 3 hours at 120C, the mixture is worked up according to Example B.

320 g of a yellowish, viscous resin, which is completely dried in vacuo at 70C, are obtained. A crude product which, according to NMR, agrees with the structure shown below, is obtained. The elementary analysis of the crude product shows:

This product was again processed as it stands. n

YN -H EXAMPLE D Adduct of 5,5-dimethylhydantoin and (3,4-epoxycyclohexyl-methyl)3,4-epoxycyclohexanecarboxylate A solution of 128 g of technically manufactured (3 ,4- epoxy-cyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate (corresponding to 0.5 mol) in 300 ml of dimethylformamide is mixed, at 120C, with 1.7 g of tetraethylammonium chloride and 128.1 g of 5,5- dimethylhydantoin 1.0 mol). The solution is stirred for 10 hours at 135C and is worked up as described in Example B. A clear, light ochre-coloured product is obtained in quantitative yield; it can easily be powdered l5 and essentially corresponds to the following structure:

EXAMPLE F Adduct of bisphenol-A diglycid and 5 ,S-dimethyl- 6-iso-propyl-5 ,6-dihydrouracil 3 l l 3 N N-ll H C C c L H C CH EXAMPLE E Adduct of 1,1-methylene-bis-dimethylhydantoin and 3,4-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate Analogously to Example 1), 384 g of the epoxide resin used in Example D, in 2,000 ml of dimethylformamide, are reacted with 804.8 g of 1,1 '-methylene-bis (5,5-dimcthyl)-hydantoin, using 5 g of tetraethylammonium chloride as the catalyst. The reaction is carried out analogously to Example D. Working up takes place as follows: The hot solution is filtered into an Erlenmeyer flask and is left to stand at C. After some hours, the adduct begins to crystallise out. The mixture CH H C C 3 l CH H EXAMPLE G Adduct of higher'molecular bisphenol-A diglycidyl ether and 5,5-dimethyl-6-isopropyl-5,6-dihydrouracil A mixture of 190 g of a commercially available high ermolecular bisphenol-A glycidyl ether resin with 2.7 epoxide equivalents/kg (Araldite B), 94 g of 5,5- dimethyl-6isopropyl-5,6-dihydrouracil and 0.5 ml of 50% strength sodium hydroxide solution is reacted at 150C, whilst stirring. After 1.5 hours, a sample taken from the batch shows an epoxide content of 0.39

is cooled at Whilst Stirring and 500 m1 of l are equivalent/kg. The mixture is then stirred for a further added, whereby a thlck crystal Paste results Thls 3 hours at 165C, in the course of which the epoxide tered and the product is suction-dried, and then dried t t drops t below 0,1 e uivalent/kg, The adduct to constant weight at C under 25 mm Hg. A pale is poured out onto a metal sheet to cool. An adduct yellow crystal powder is obtained, the yield being 1,048 mixture of predominantly the following structure is obg (corresponding to 88.1% of theory). 69 tained:

0 o H -N N CH C|HCH O @413 @4) cH cH cH N H N & HC 0 O H CH CH HCHC C/ H.c l 3 3 3 3 I H H C In this formula, n denotes the average degree of polymerisation (also of the initial epoxide resin) of about 6.

EXAMPLE H Addition of ethylene oxide to the product from Example B 220 g of the adduct manufactured according to Example B (0.361 mol) and 1.4 g of lithium chloride are dissolved in 540 ml of dimethylformamide. A solution of 43.7 g of ethene oxide (0.992 mol) in 250 ml of dimethylformamide is added to the first solution at room temperature, whilst stirring gently. The mixture is warmed to 100C over the course of 2 hours and stirred for a further 3 hours at this temperature. Thereafter it I is cooled to C, filtered and concentrated at C/20 mm Hg, and dried to constant weight at C/0.l mm Hg. 250 g of a clear, highly viscous, light ochrecoloured polyol of theory) are obtained, of which the NMR spectrum agrees with predominantly the following structure:

EXAMPLE 1 Addition of ethylene oxide to the product from Example C Analogously to Example H, a solution of 200 g of the adduct manufactured according to Example C and 1.0 40

g of lithium chloride in 500 ml of dimethylformamide is treated, at room temperature, with a solution of 27.5 g of ethylene oxide in 100 ml of dimethylformamide and the procedure described in Example H is followed.

g of a clear glassy tetraalcohol (95% of theory) are obtained and are glycidylated in the crude form.

EXAMPLE J Addition of ethylene oxide to the product from Example D 676 g of the adduct manufactured according to Example D are dissolved in 1,300 ml of dimethylformamide. After addition of 1.7 g of lithium chloride,

234.5 g of ethylene oxide in 600 ml of dimethylformamide are added and the procedure analogous to Example H is followed. 690 g of a product (87%) are obtained, in which the N-H groups of the formula given in Example D are very largely replaced by the structure NCH -CH -OH.

EXAMPLE K Adduct of 2 mols of 5,5-diethylbarbituric acid and 1 mol of 3-( 3 ',4'-epoxycyclohexyl )-2,4-dioxaspiro-( 5 ,5 )-9, 10- epoxyundecane A solution of 64.3 g of technically manufactured 3- (3 ',4'-epoxycyclohexyl)-2,4-dioxaspiro-( 5 ,5 )-9 l 0- HC 0 3 CH3 epoxyundecane (93.6% strength) (0.226 mol) and 0.75

A c c n l A 2 5 z 2 s 7 S cn o EXAMPLE 1 Adduct of l,3-diglycidyl-5,S-dimethylhydantoin and 5,5-dimethylhydantoin 390.9 g of technically manufactured l,3-diglycidyl 5,5dimethylhydantoin (92.5% strength) (1.5 mols) and 5.0 g of tetraethylammonium chloride are dis l3 l4 solved in 75 ml of dimethylformamide and this solution take place analogously to Example K. is stirred at l 10C. 384.5 g of 5,5-dimethyl-hydantoin 44 g of the corresponding adduct are obtained in the (3.0 mols) are then added with vigorous stirring. The form of a light powder (66.7% of theory). reaction becomes strongly exothermic so that the heat- EXAMPLE mg bath 1S removed and replaced by an ice water bath; 5 the temperature is thus regulated to 112C Adduct of 1,1-methylene-bis(5,5-dimethylhydantoin) When the exothermic effect has subsided, the mixture i is stirred for a further 3 hours at l 15C. The solvent is 11kmethylenebm3-g1yCldyL5jdlmethylhydamom) then distilled off at 100C/30 mm Hg and the product A miXtul'e 0f 205-5 g of y is dried at 100c/0.2 mm Hg. 765 g of a pale yellow, y y y y epOXide q brittle glass, which can easily be Powdered, are oblemS/kg) (0'54 mol) 289's g of lll'methylene' mined bis(5,5-dimethyl-hydantoin) (1.08 mols), 1.8 g of tetraethylammonium chloride and 750 ml of dimethylformamide is stirred at 110 120C; the reaction becomes exothermic and is carried out according to Example K, and the product is worked up according to Example K.

488 g of a light yellow powder (98.6% of theory) are 335 g of technically manufactured l-glycidyl-3- Obtainedglycidyloxypropyl-5,S-dimethylhydantoin (epoxide EXAMPLE P content 5.97 equivalents/kg) (1 mol) and 3.3 g oftetraethylammonium chloride are dissolved in 1 litre of dimethylformamide and 258.2 g of 5-isopropylhydantoin (2 mols) are added at 120C, whilst stirring. The reac- A mixture of g of the liv'methylene'bis'w' tion becomes exothermic and the mixture is kept at g1yCidYl-5754imethy1hydantoinl q in 120C for a total of 5 hours by periodic cooling. Workample g of tetraiethylammomllm 9111mm and ing up takes place analogously to Example 11 593 g 50.5 g of 6-methy1uracil (0.4 mol) 1S stirred for 10 hours at 120C, whereby a clear, colourless solution 18 (theory: 583 g) of a hght brown powder memng at produced" this is worked up analogously to Example K. 486C (Mettler FP 51) are obtained. The elementary I 127 g (100% of theory) of a light yellow, glassy submalysls of the Crude product Shows stance are obtained. This can be recrystallised from alcohol. 104 g (82.2% of theory) of fine crystals, melting at 176C (Mettler PF 51) are obtained.

EXAMPLE M Adduct of 5-isopropylhydantoin and lglycidyl-3-glycidyl-2-oxyn-propyl-5 ,5- dimethylhydantoin (molar ratio 2:1

Adduct of 6methy1uraci1 and 1 ,1 '-methylene-bis-( 3-glycidy1-5 ,S-dimethylhydantoin) Found Calculated 7.3% H 7.3% H EXAMPLE Q I 97: N 44 N Adduct of 5,5-dimethylhydantoin and 2,2 ,6,6-tetra( glycidylcarboxy-ethyl )cyclohexanone 123.8 g of 2,2,6,6-tetra(glycidyl-carboxy-ethyl)- Accordmg to the H'NMR Spectrum, the crude product cyclohexanone (epoxide content: 5.9 equivalents/kg) only retains a trace of dimethylformamide. (0.184 mol), 94.1 g of 5,5-dimethylhydantoin and 200 The product has the following structure: ml of dimethylformamide are stirred for 5 hours at 125 CH3; 3 CH3 CH/CH3 org/ 0 o o CH,

CIH" H N N CH -CHCH -N N 2- 2 2N N H Y Y Y o o 0 55 I EXAMPLE N 130C; the reaction is initially slightly exothermic. Adduct of The working up of the product takes place analogously 1,1-methylene-bis-(5,5-dimethyl-5,6-dihydrouracil) to Example K. 210 g of a highly viscous liquid are oband tained; this crude product still contains a trace of dil-glycidyloxymethyl-3-glycidyl-5,S-dimethylhydantoin methylformamide.

l t' 2: 1 1 (mo ar ra 1o EXAMPLE R A so ution of 22.2 g of l-glycidyloxymethyl-3- g1ycidyl 5a5 dimethylhydamoin (973% strength) 2:1 adduct of lli3dlglycidyl5l; 5-d}:met{1yl-hydantom (0.077 mol) and 0.2 g of tetraethylammonium chloride ydrogenated eno in ml of dimethylformamide is mixed, at C, with The following mixture is stirred for 4.5 hours at 45.6 g of 1,1'-methylene-bis(5,5-dimethyl-5,6- 120C: 5 12.8 g of 1,3-diglycidyl-5,5dimethylhydantoin dihydrouracil) (0.154 mol). The reaction, and working (2.0 mols), 240.4 g of hydrogenated bisphenol A (1.0

manufacture of the tetraglycidyl compound.

HCI HC 0 /l l l 2:1 adduct of 5,5-dimethylhydantoin and the diglycidyl ether of hydrogenated bisphenol A MANUFACTURE OF THE POLYGLYCIDYL COMPOUNDS ACCORDING TO THE INVENTION EXAMPLE (1) A mixture of 63.6 g of the adduct manufactured ac cording to Example A (0.1 mol; 0.4 equivalent of reactive H), 370 g of epichlorohydrin and 0.3 g of tetramethylammonium chloride is stirred for 140 minutes at 1 l7l 18C. A sample withdrawn from the batch and freed of all volatile constituents then contains 1.88 epoxide equivalents/kg.

The dehydrochlorination is carried out as follows: An azeotropic circulatory distillation is set up, by application of vacuum (6090 mm Hg) in such a way that a vigorous distillation proceeds in the reaction mixture at 60C. 38.4 g of strength sodium hydroxide solu tion (0.48 mol) are now added dropwise over the course of 150 minutes, whilst stirring vigorously. In the course thereof, the water present in the reaction mixture is continuously removed from the batch, and separated off. Thereafter, distillation is allowed to continue for a further 15 minutes, the residue is cooled to 30C, and the sodium chloride produced in the reaction is filtered off. The filtrate is then washed with 50 ml of water to remove the last traces of caustic alkali and salt and the organic phase is concentrated on a rotary evaporator at 60C/l5 mm Hg. 50 ml of water are now added and traces of epichlorohydrin and the like are distilled off together with this water. Thereafter, the same process is repeated with 50 ml of toluene to remove remnants of water. The residue is then treated at 120C/0.2 mm Hg until it reaches constant weight.

82.7 g (96.2% of theory) of a brittle, clear, pale yellow resin of epoxide content 4.30 equivalents/kg (92.7% of theory) are obtained. The total chlorine content is l.l%. The new tetraglycidyl compound has a softening point of 66C (according to Kofler) and essentially is present in the following structure:

EXAMPLE (2) Glycidylation of the adduct according to Example B Analogously to Example (1), 503 g of the adduct manufactured according to Example B (0.84 mol) are stirred with 2,495 g of epichlorohydrin (26.97 mols) and 5.6 g of tetraethylammonium chloride for 3 hours at C. Thereafter, dehydrochlorination is carried out, as described in Example l with 350.5 g of 50% strength sodium hydroxide solution, under azeotropic circulatory distillation and whilst stirring vigorously. Working up and purification are also carried out analogously to Example l 632 g (97% of theory) ofa very viscous tetraglycidyl compound are obtained, of epoxide content 4.26 epoxide equivalents/kg 86.4% of theory).

EXAMPLE (3) Glycidylation of the adduct according to Example 1 179.8 g of the crude tetraalcohol manufactured ac cording to Example I (0.186 mol) are treated with 552 g of epichlorohydrin (5.967 mols) and 0.9 g of tetraethylammonium chloride analogously to Example A. The dehydrochlorination is carried out with 77.8 g of 50% strength sodium hydroxide solution, again as described. After working up and purification analogously to Example 1), 189.2 g of a very viscous, clear, light yellow tetraglycidyl compound (94% of theory) are obtained, of which the epoxide content is 3.4 epoxide equivalents/kg 100% of theory). The total chlorine content is 2%.

EXAMPLE (4) Glycidylation of the adduct according to Example J 656.5 g of the tetraalcohol obtained according to Example J (1.1 mols) and 4 g of tetraethylammonium chloride in 3,330 g of epichlorohydrin (36.0 mols) are treated analogously to Example (1). The dehydrohalogcnation is carried out with 456.6 g of 50% strength aqueous sodium hydroxide solution (5.71 mols) in the manner described above. The working up again takes place analogously to Example A. 704 g (78% oftheory) of the desired tetraglycidyl compound,-of which the ep- 17 oxide content is 4.69 epoxide equivalents per kg (95.8% of theory), are obtained. The total chlorine content is 1.6%. The nitrogen content is 6.7% (theory, 69%) EXAMPLE Glycidylation of the adduct from Example E 789 g of the adduct manufactured according to Example E (1 mol) together with 6.6 g of tetraethylammonium chloride are treated with 2,950 g of epichlorohydrin according to Example (1). Both the dehydrochlorination with 410 g of 50% strength aqueous sodium hydroxide solution and the subsequent working up are also carried out according to Example (1). 951 g (95% of theory) of a solid, clear resin with 3.32 epoxide equivalents/kg (82.6% of theory) are obtained. The softening range is about 92C.

EXAMPLE (6) Glycidylation of the adduct from Example F As described in Example l), 345 g of the adduct from Example F, 3.2 g of tetraethylammonium chloride, 1,420 g of epichlorohydrin and 199.5 g of 50% strength aqueous sodium hydroxide solution are reacted, and worked up, under the conditions described.

383.2 g of the desired tetraglycidyl compound (94.8% of theory), containing 4.08 epoxide equivalents/kg (86% of theory), are obtained. The softening point is about 58C.

EXAMPLE (7) Glycidylation of the adduct from Example G 182 g of the adduct manufactured according to Example G are treated with 1.3 g of tetraethylammonium chloride and 1,200 g of epichlorohydrin according to Example (1). The dehydrochlorination with 67.3 g of 50% strength aqueous sodium hydroxide solution, and the further working up, also take place as described above.

216.2 g ofa solid resin (99% of theory) with an epoxide content of 3.8 equivalents/kg are obtained.

EXAMPLE (8) Tetraglycidyl compound of the product according to Example H Analogously to Example l a solution of 139.4 g of the tetraalcohol manufactured according to Example H (0.2 mol) is reacted with 444 g of epichlorohydrin (4.8

mols) and 0.9 g of tetraethylammonium chloride by first stirring for 2 hours at 90C.

Dchydrohalogenation is then carried out with 83.5 g of 50% strength sodium hydroxide solution under azeotropic circulatory distillation, as described in more detail in Example 1). The working up and purification of the product take place according to Example 1 170.7 g of a yellow, clear, viscous resin (93.9% of theory), of epoxide content 4.35 equivalents/kg (98.9% of theory), are obtained. The total chlorine content is 1.5%.

EXAMPLE (9) Tetraglycidyl compound of the product according to Example K A solution of 137.7 g of the adduct manufactured ac cording to Example K, of melting point 672C (0.217 mol) and 1.9 g of 50% strength aqueous tetramethyl- Found Calculated (C H N O 7.4% H 7.3% H 6.7% N 6.5% N

14% C1 0.0% Cl Example 10) Tetraglycidylation of the product according to Example 1 621 g of the adduct manufactured according to Example l (1.25 mols) are treated analogously to Example 1) with 3,700 g of epichlorohydrin, 10 g of 50% strength aqueous tetramethylammonium chloride solution and then with 460 g of 40% strength aqueous sodium hydroxide solution (5.75 mols); the working up of the product is carried out appropriately.

762.2 g (84.6% of theory) of a brown tetraglycidyl compound with 4.96 epoxide equivalents/kg (89.3% of theory) and 1.2% of total chlorine, which softens at room temperature, are obtained.

EXAMPLE l l Tetraglycidylation of the product according to Example M The following substances are reacted analogously to Example 1): 563.0 g of the adduct from Example M (0.966 mol), 2,860 g of epichlorohydrin (30.9 mols), 8.5 g of 50% strength aqueous tetramethylammonium chloride and 356 g of 50% strength aqueous sodium hydroxide solution.

Working up takes place as described above and a highly viscous brown resin, of epoxide content 4.37 equivalents/kg (88.1% of theory), is obtained in 92% yield (715.7 g); the total chlorine content is 2%.

EXAMPLE (12) Tetraglycidylation of the product according to Example N The following are reacted analogously to Example (1): 36 g of the adduct from Example N (0.042 mol), 124 g of epichlorohydrin (1.34 mols), 0.7 g of 50% strength aqueous tetramethylammonium chloride and 15.4 g of 50% strength aqueous sodium hydroxide solution (0.19 mol).

After the customary working up, 28 g (62%) of a light brown, tacky resin are obtained. Epoxide content 3.08 equivalents/kg (83% of theory).

EXAMPLE (l3) Tetraglycidylation of the product according to Example 0 The following are reacted according to Example (1): 0.315 mol of adduct according to Example 0 (289 g),

19 1O mols of epichlorohydrin (925 g), 2.8 g of 50% strength aqueous tetramethylammonium chloride and 1.45 mols of 50% strength sodium hydroxide solution (1 16 g). Working up takes place as mentioned and a light yellow, solid tetraglycidyl compound is obtained, of softening point 67C (according to Kofier). The epoxide content is 3.71 equivalents/kg (94.6% of theory).

EXAMPLE 14) Tetraglycidyl compound of the product according to Example C The following were reacted analogously to Example (1 444.6 g of adduct, manufactured according to Example C (0.5 mol), 1,480 g of epichlorohydrin (16 mols), 8.8 g of 50% strength aqueous tetramethylammonium chloride and 184 g of 50% strength sodium hydroxide solution (2.3 mols).

The product is isolated according to Example 1) and 441.4 g (81%) of a solid, light brown resin are obtained, softening at 78C (Kofler) and having an epoxide content of 3.41 equivalents/kg (93.9% theory).

EXAMPLE (15) Tetraglycidyl compound of the product according to Example P The following are reacted analogously to Example (1): 72.0 g of the adduct according to Example P (0.114 mol), 474.0 g of epichlorohydrin (5.125 mols), 4.6 g of tetramethylammonium chloride, 50% strength in water and 42.4 g of 50% strength aqueous sodium hydroxide solution (0.53 mol).

The customary working up yields 76.0 g (77.9% of theory) of the tetraglycidyl compound of epoxide content of 3.81 equivalents/kg (81.5% of theory); the compound softens at 103C (Kofler).

EXAMPLE 16) Polyglycidyl compound of the product according to Example Q EXAMPLE l7:

Glycidylation of the adduct manufactured according to Example R 736 g of the adduct manufactured according to Example R, having an epoxide content of 2.49 equivalents/kg 1 mol), are reacted with 2,738 g of epichlorohydrin and g of 50% strength aqueous tetraethylammonium bromide, the procedure according to Example I being followed, and the dehydrohalogenation being carried out with 197 g of 50% strength aqueous sodium hydroxide solution, in the manner described above.

Working up also takes place according to Example 1, and 302.3 g (36.3% of theory) of a clear, yellow resin 20 of medium viscosity, of which the epoxide content corresponds to 4.68 equivalents/kg (97.5% of theory), are obtained.

EXAMPLE l8:

Glycidylation of the adduct manufactured according to Example S The following are reacted analogously to the description in Example 1: 750 g of the adduct according to Example S (1 mol), 4,163 g of epichlorohydrin (45 mols), 20 g of tetraethylammonium chloride (50% strength, aqueous), and 400 g of 50% strength sodium hydroxide solution (5 mols).

Working up also takes place according to Example 1 and 810 g (97.2% of theory) of a highly viscous resin of epoxide content 4.07 equivalents/kg (84.8% of theory) are obtained.

B EXAMPLES OF APPLICATIONS Example I 48 parts of the epoxide resin manufactured according to Example 4), with 4.69 epoxide equivalents/kg, are mixed with 55 of hexahydrophthalic anhydride and stirred at C to give a homogeneous melt. This mixture is poured into aluminium moulds of 4 mm wall thickness which have been prewarmed to C and is cured in 6 hours at 100C and 2 hours at C and 10 hours at C. Mouldings having the following properties are obtained:

Flexural strength (VSM 77,103) 15.816.8 kp/mm Deflection (VSM 77,103) 6 11 mm EXAMPLE I] 64 parts of the tetraglycidyl compound manufactured according to Example 8), containing 4.35 epoxide equivalents/kg, are mixed with 37 parts of hexahydrophthalic anhydride at 80C and the mixture is cured in an aluminium mould of 4 mm wall thickness in 4 hours at 120C and 15 hours at C. A clear, transparent moulding having the following properties is obtained:

Flexural strength (VSM 77,103) 15.8-17.2 kp/mm Deflection (VSM 77,103) 810 mm Impact strength (VSM 77,105) 13.3 cmkp/cm Heat distortion point according to Martens Water absorption (DIN 54,458) (4 days/20C) EXAMPLE 111 100 parts of the epoxide resin obtained according to Example 1 1 are mixed with 75 parts of hexahydrophthalic anhydride at 80C to give a homogeneous melt and the mixture is cured in an aluminium mould (4 mm sheets) in 4 hours/80C and 16 hours/140C. The mouldings thus obtained have the following mechanical properties:

Flexural strength (VSM 77,103) 16 kp/mm Heat distortion point according to Martens (DIN 54,458) 146-147C Water absorption (4 days/20C) 0.65?!v EXAMPLE IV -Continued l parts of the epoxide resin manufactured accord- CH. [:H 0 ing to Example 1 l are processed with 75 parts of hexahydrophthalic anhydride as described in Example III, 7 I

and the mouldings obtained show the following proper- 2 ties: C Y ll O Flexural strength (VSM 77.103) l4-36 (mean value from 5 mcasurements=24) I kp/mm Hcut distortion point according to Maflcns (DIN 54 458) l l9l22C Water absorption (4 days/C) 0.6% I

EXAMPLE V 100 parts of epoxide resin from Example 9 are treated with 70 parts of hexahydrophthalic anhydride according to Example Ill. Castings having the following 20 properties are obtained:

Flcxural strength (VSM 77,l03) 23.0 kp/rru'n Heat distortion point according to Martens (DlN 54.458) l25l26C 25 Water absorption (4 days/20C) 0.44%

(1 hour/ 100C) 041% wherein a and b are identical or different and denote either 0 or l' Wh i 1 1s :1 i iii l com ound of the formula R; ls hydrogen or methyl;

' p yg y y p and R is one of the radicals A CH CHCH R'CH -CH 7CH CH CH CH CH 2! 3 Z 2 o (I) l o cH ci\1 cH ior C CH 2 CH CH CH CH 2. Polyglycidyl compound according to claim 1 chawherein A is an organic radical of the formula racterised m that R 1n the formula II denotes one of the radicals 0 CH1; CH:| CH3 CH3 0 40 n C ---C CH; CH! I I l -N N-(H N N CHC CH; CH.

ll (H, CH, 0 and II --c CHu v C /CH2-CH2\ H --N\ N(H.:-(TH() \CHFCH2 2 F 3. Polyglycidyl compound of the formula H C H C H C H c CH3 3 CH 3 CH 3 CH 3 t 3 3 3 o I l 0 /l /l H-1((H(H,- N N CH -(lZH-CH- N N cH, N NCH (lIH--CH. N N--CH2CHCH2 0 Y 1 Y E Y 2 2 o (11 o o C H o H L TH 23 4. Polyglycidyl compound of the formula I CH 24 5. Polyglycidyl compound of the formula Y n 0 W0

Claims (5)

1. A POLYGLYCIDYL COMPOUND OF THE FORMULA

2. Polyglycidyl compound according to claim 1 characterised in that R2 in the formula II denotes one of the radicals

3. Polyglycidyl compound of the formula

4. Polyglycidyl compound of the formula

5. Polyglycidyl compound of the formula